Sustainable Hyperbranched Functional Materials via Green Polymerization of Readily Accessible Levoglucosenone‐Derived Monomers

Abstract

The homopolymerization in basic conditions of the recently reported bis( -lactone), 2H-HBO-HBO, is herein described for the first time. The solvent-free polymerization of this pentafunctional levoglucosenone (LGO) derivative affords fully renewable poly(vinyl-ether lactone) copolymers with a highly hyperbranched structure. This investigation stems from the polycondensation trials between 2H-HBO-HBO and di(methyl carbonate) isosorbide (DCI) that fails to give the anticipated polycarbonates. Such unexpected behavior is ascribed to the higher reactivity of the 2H-HBO-HBO hydroxy groups toward its , -conjugated endocyclic C═C, rather than the DCI methylcarbonate moieties. The different mechanistic scenarios involved in 2H-HBO-HBO homopolymerization are addressed and a possible structure of poly(2H-HBO-HBO) is suggested. Furthermore, the readily accessible (S)--hydroxymethyl-, -butenolide (HBO) is also polymerized for the first time at a relatively large scale, without any prior modification, resulting in a new hyperbranched polymer with an environmental factor (E factor) ≈0. These new HBO-based polymers have a great potential for industrial-scale production due to their interesting properties and easy preparation via a low-cost, green, and efficient process.

Fully renewable photocrosslinkable polycarbonates from cellulose-derived monomers

“…), the 13 C spectrum displayed only three CO signals with intensity ratios of 1 : 2 : 1 corresponding to the endo – endo , endo – exo / exo – endo , and exo – exo carbonate groups, respectively. 54…”

“…ratios of 1 : 2 : 1 corresponding to the endo-endo, endo-exo/exoendo, and exo-exo carbonate groups, respectively. 54 In an attempt to quantitatively determine the relative fractions (in %) of the repetitive units of the PC structures, the deconvolution of the 1 H NMR spectra was performed to separate the overlapping peaks and determine the corresponding area and intensity of each signal.…”

Sustainable valorisation of renewables through dialkyl carbonates and isopropenyl esters

“…149 Allais, Fadlallah et al reported on the copolymerisation between ISB, DMC and bis-γ-lactone, a monomer derived from levoglusenone, observing almost exclusive fast homopolymerisation of the bis-γ-lactone comonomer. 150 DACs/diols polycondensation represents a promising strategy for the preparation of commercially relevant renewable-based polyesters. It is likely that this technology will reach high TRLs in the next 10-15 years, therefore, the commercial relevance of this process must be combined with a detailed assessment of its economical and environmental viability, as well as with an evaluation of the toxicity, ecocompatibility and end-of-life fate of the resulting polyesters.…”

“…149 Allais, Fadlallah et al reported on the copolymerisation between ISB, DMC and bis-γ-lactone, a monomer derived from levoglusenone, observing almost exclusive fast homopolymerisation of the bis-γ-lactone co-monomer. 150…”

Bio-based polycarbonates: progress and prospects

“…DCI can be obtained in high yield by methoxycarbonylation of isosorbide in the presence of DMC, and it is one of the potential monomers for the synthesis of functional PC. 92,120 Recently, Aricò et al 121 used the levoglucosyl triol monomer citrate triol (triol-citro) to achieve polycondensation with DCI to synthesize PC containing both linear and dendritic units. The novel PC is composed entirely of bio-derived groups with citronellol side chains, leading to the cross-linking of the side chains induced by UV light irradiation.…”